3, 5, 6-substituted hydrouracils



United States Patent C) 3,360,523 3,5,6-SUBSTITUTED HYDROURACILS HarveyM. Loux, Hockessin, DeL, assignor to E. I. du Pont de Nemours andCompany, Wilmington, Del., a corporation of Delaware No Drawing.Original application June 17, 1964, Ser. No. 375,958, now Patent No.3,322,526, dated May 30, 1967. Divided and this application Mar. 30,1967, Ser. No.

9 Claims. (Cl. 260-260) ABSTRACT OF THE DISCLOSURE The compounds of theinvention are of a class of hydrouracils bearing substituents at the 3,5, and 6 ring positions which are useful herbicides. Typical examplesare 5,5 dichloro-3-isopropyl-6-methoXy-6-methylhydrouracil and 5,5dichloro-3-cyclohexyl-6-methoxy 6 methylhydrouracil. Also a part of theinvention are phenol and substituted phenol complexes of the substitutedhydrouracils.

CROSS-REFERENCE This application is a division of copending applicationS.N. 375,958, filed June 17, 1964, issued as Patent No. 3,322,526, whichin turn is a continuation-in-part of application S.N. 158,567, filedDec. 11, 1961, and now abandoned. Copending application S.N. 375,958claims a class of substituted hydrouracils including the novel compoundsof this invention as well as additional compounds as herbicides.

DESCRIPTION OF INVENTION This invention relates to substitutedhydrouracils. It is more particularly directed to methods andcompositions for using hydrouracils as herbicides.

The hydrouracils to be used according to this invention are those havingthe formula R is alkyl of 1 through 10 carbon atoms, substituted alkylof 1 through 8 carbon atoms, aryl of through 10 carbon atoms,substituted phenyl, aralkyl of 5 through 13 carbon atoms, substitutedaralkyl of 5 through 13 carbon atoms, alkenyl of 3 through 8 carbonatoms, cycloalkyl of 3 through 12 carbon atoms, substituted cycloalkylof 3 through 13 carbon atoms, cycloalkenyl of 4 through 12 carbon atoms,substituted cycloalkenyl of 4 through 13 carbon atoms, cycloalkyl alkylof 4 through 13 carbon atoms, cycloalkenyl alkyl of 5 through 13 carbonatoms (substituted cycloalkyl) alkyl of 5 through 14 carbon atoms, or(substituted cycloalkenyl)alkyl of 5 through 14 carbon atoms;

R is hydrogen, chlorine, fluorine, bromine, iodine, methyl, ethyl,propyl, butyl, methoxy, ethoxy, propoxy, butoxy, nitro, alkoxymethyl of2 through 6 carbon atoms, hydroxyalkyl of 1 through 6 carbon atoms,alkylthio of 1 through 4 carbon atoms, or methylthiomethyl;

R is chlorine, bromine, fluorine, hydrogen, methyl, or

ethyl;

R is hydrogen, chlorine, hydroxy, alkoxy of 1 through 6 carbon atoms,halo alkoxy of 1 through 6 carbon atoms, substituted or unsubstitutedacyloxy of 1 through 6 carbon atoms, methyl, or ethyl;

R is hydrogen, chlorine, bromine, alkyl of 1 through 5 Patented Dec. 26,1967 carbon atoms, chloralkyl of 1 through 4 carbon atoms, bromoalkyl of1 through 4 carbon atoms, or allroxy of 1 through 5 carbon atoms; and

R is hydrogen, chlorine, bromine, substituted or unsubstituted alkyl of1 through 5 carbon atoms, or alkenyl of 2 through 5 carbon atoms;

with the proviso that R and R can be taken together to form a divalentalkylene bridge of the formula (CH where n is 3, 4, or 5 and with thefurther proviso that said hydrouracil compounds cannot exceed amolecular weight of 500.

For R the term substituted alky is intended to include such radicals as:

bromoalkyl of 1 through 5 carbon atoms chloroalkyl of 1 through 5 carbonatoms hydroxyalkyl of 1 through 5 carbon atoms alkoxyalkyl of 2 through5 carbon atoms cyanoalkyl of 2 through 5 carbon atoms 1 Within thisscope is a group of novel compounds of the formula H R: RiN o ka, E R5where R is alkyl of 3 through 6 carbon atoms, cycloalkyl of 3 through 12carbon atoms, substituted cycloalkyl of 3 through 13 carbon atoms,cycloalkyl alkyl of 4 through 13 carbon atoms, or (substitutedcycloalkyl) alkyl of 5 through 14 carbon atoms;

R, is chlorine, bromine, fluorine, nitro, methyl, ethyl,

hydroxymethyl, methoxymethyl, ethoxymethyl, methoxy, or hydrogen;

R is chlorine or bromine;

R, is alkoxy of 1 through 6 carbon atoms, and

R is methyl or ethyl.

For R in Formulae 1 and 2 above, the term substituted alkyl is intendedto include such radicals as bromoalkyl of 1 through 8 carbon atoms,

chloroalkyl of 1 through 8 carbon atoms,

hydroxyalkyl of 1 through 8 carbon atoms,

alkoxyalkyl of 2 through 8 carbon atoms,

alkoxy carbonyl alkyl of 3 through 8 carbon atoms, and cyanoalkyl of 2through 8 carbon atoms.

Similarly, the terms aryl and substituted phenyl embrace radicals suchas nitrochlorophenyl,

nitrophenyl,

dichloronitrophenyl,

chloroalkoxyphenyl of 7 through 11 carbon atoms, trifluoromethylphenyl,

tetrahydronaphthyl, and

in-denyl.

The terms aralky and substituted aralky are intended to include suchradicals as The terms cycloalkyl, cycloalkeny, alky and cycloalkenylalkyl will include cycloalkyl cyclohexyl,

cyclohexenyl,

cyclohexylalkyl,

cyclohexenylalkyl,

cyclopentyl,

cyclopentenyl,

cyclopentylalkyl,

cyclopentenylalkyl,

norbornyl,

norbornenyl,

norbornylalkyl,

norbornenylalkyl,

bicyclo(2,2,2) octyl, bicyclo(2,2,2)octenyl,

bicyclo (2,2,2 octyl'alkyl, bicyclo(2,2,2)octenylalkyl, cyclopropyl,

cyclobutyl,

cyclo'butylalkyl,

cyclobutcnyl,

cyclobutenylalkyl,

hexahydroindanyl,

tetrahydroindanyl,

hexahy-droindenyl,

hexahydroindenyl alkyl, tetrahydroindanyl alkyl, hexahydroindanyl alkyl,hexahydro-4,7-methanoindenyl, tetrahydro-4,7-methanindanyl,hexahydro-4,7-methanoindanyl, hexahydro-4,7-methanoindenyl alkyl,tetrahydro-4,7-methanoindanyl alkyl, hex-ahydro-4,7-methanoindanylalkyl, decahydronaphthyl, decahydronaphthyl alkyl, tetrahydronaphthyl,tetrahydronaphthyl alkyl, decahydro-1,4-methanonaphthyl,decahydro-1,4-methanonaphthyl alkyl, octahydro-l,4-methanonaphthyl,octahydro-1,4-methanonaphthy1 alkyl, decahydrol,4-5,8-dimethanonaphthyl, decahydro-1,4-5,8-dimethanonaphthyl alkyl,octahydro-1,4-5,8-dimethanonaphthyl, andoctahydro-l,4-5,8-dimethanonaphthyl alkyl, tetrahydrofurfuryl.

These cyclic substituents can be further substituted with alkyl groupsof 1 through 4 carbon atoms, methoxy, chlorine, or bromine.

Certain dihydrouracils of Formula-1 also form water stable, novelcomplexes with phenol and substituted phenols. These complexes have theformula X o R1 RIN R3 m-l l where R R R R and R are as defined inFormula 2,

X is hydrogen, chlorine, nitro, alkyl of 1 through 3 carbon atoms,bromine or alkoxy of l to 3 carbon atoms,

Y is chlorine or alkyl of 1 through 3' carbon atoms,

in is a number 1 through 5, and

n is 1 or 2.

These complexes are also herbicidal, and in this respect, have someadvantages over the uracils per se, viz., higher solubility in oils andsolvents. They are formulated into herbicidal compositions in the sameway as are the uracils themselves.

The hydrouracils of this invention can be prepared according to methodswell known to those familiar with pyrimidine chemistry.

One method involves the addition of moieties across the double bondbetween the 5- and 6-positions of the uracil starting material. Thestarting materials used according to this method have the generalstructure O H BIN l-Rz 0* R5 Where R R R and R are defined as inFormula 1. Preparation of these compounds is described in detail inPatents Nos. 3,235,357, issued Feb. 15, 1966; 3,235,358, issued Feb. 15,1966; 3,235,362, issued Feb. 15, 1966; and 3,235,363, issued Feb. 15,1966.

Hypohalous acids and organic hypohalites derived from bromine andchlorine, such as alkyl and acyl hypohalites, add across the double bondaccording to the following equation:

R R and R are defined as in Formula 1 and R is hydrogen or alkyl of 1-5carbon atoms,

R, is hydrogen, alkyl of 1 through 6 carbon atoms, acyl of 1 through -6carbon atoms; and

X is chlorine or bromine.

When R in the product is hydrogen or alkyl, the R7OX reactant isprepared according to the following equation:

When R is acyl, it is prepared according to the following equation:

R7OH7+X2 R'7OX+R7X The preparation of this reactant and its reactionwith the uracil starting material is most easily carried out in one stepby dissolving or suspending the uracil starting material in an excess ofRqOH or RqOR used as a liquid medium, and passing in a stoichiometricamount of a halogen. The reaction is exothermic and it is necessary tocool the reaction vessel to keep it at room temperature.

In Equation 5, when the 5-position in the uracil starting material issubstituted with hydrogen, the resulting compound will have two halogenatoms in the 5-position. In this case, two moles of halogen must beused. When the substituent in the 5-position of the uracil startingmaterial is anything else, only one halogen will be added in the5-position of the resulting product, as is illustrated in Equation 5.

For a more detailed discussion of the above, see D. J. Brown, ThePyrimidines, Interscience, 1962, pp. 172-174, and I. Am. Chem. Soc. 59,2436 (1937).

Hydrogen can be added across the double bond by catalytic hydrogenation.This is accomplished by hydrogenating the uracil starting material in asolvent such as ethanol or dioxane under a pressure of about 1700 poundsper square inch and a temperature of about 220 C., using a catalyst suchas ruthenium or platinum. This is illustrated by the following equation:

R is as defined in Formula 1,

R is alkyl of 1-5 carbons, or hydrogen,

R is hydrogen, alkyl of 1-5 carbons, alkoxy of 1-5 carbons,hydroxyalkyl, alkoxyalkyl, or fluorine,

R is hydrogen, alkyl of 1-5 carbons, or alkoxy of 1-5 carbons;

- ll H R5 R2 R 1 3 No-o-oooorn rnNoo V H Rs R4 R: O: N R- Re where R R Rand R are defined as in Formula 1;

R is hydrogen, alkyl of 1 through 5 carbon aotms, or alkoxy of 1 through5 carbon atoms, and

R is hydrogen, alkyl of 1 through 5 carbon atoms, or

alkenyl of 2 through 5 carbon atoms.

This reaction is carried out by mixing the reactants in an inert solventsuch as benzene, toluene, Xylene, or cyclohexane. The reaction isspontaneous and exothermic. The solvent is stripped ofi under reducedpressure and the residue is suspended in a dilute (6 N) aqueous acidsuch as hydrochloric or sulfuric, in a ratio of about one part ofresidue to each 20 parts of acid.

In some cases hydroxide or alkoxide efiects ring closure.

The mixture is boiled. for approximately one hour and then evaporated todryness under reduced pressure to give the desired hydrouracil, whichcan, if required, be recrystallized from water or such solvents asalcohol, acetonitrile, or nitromethane.

A third method for preparing dihydrouracils of this invention involvesthe addition of a substituted urea to an tt-unsaturated acid orderivative thereof according 6 to Equation 8.

I R2 0 R4 R) O H g l y: R1N RiNH NHi-i- /o=c- OH L R5 0: N H R5 where Rand R are defined as in Formula 1, R is hydrogen, alkoxy of 1-6 carbons,and R is hydrogen, alkyl of l-5 carbons,

with the proviso that R and R can be taken together to form (CH where nis 3, 4, or 5.

This reaction is carried out by heating a mixture of the urea and thea,,8-unsaturated compound at 200-250 C. for 1-3 hours. The dihydrouracilis obtained as a glassy material which may be purified by conventionalprocedures.

This method is further described in D. J. Brown, The Pyrimidines,Interscience, 1962, pp. 431-434, and Chem. Ber. 34, 3751 (1901).

A fourth method for preparing certain hydrouracils of this inventioninvolves the addition of functional groups to hydrouracils which havebeen prepared according to the aforementioned procedures. Accordingtothis method, functional groups can be modified and exchanged withoutdisturbing the dihydrouracil nucleus. This is demonstrated by thefollowing equation:

This reaction is carried out by dissolving the dihydrouracil startingmaterial in the reagent-solvent in a ratio of about 1 to 10. In thecases of HCl and HBr, an inert solvent can be used. About 1 to 5%, byweight .of the starting hydrouracil, of an acid catalyst should also bepresent. Suitable catalysts are anhydrous hydrochloric acid, sulfuricacid, and para toluene sulfonic acid. The reactants are allowed to standat room temperature for from 5 to 25 hours. The product is isolated bystripping olT the solvent under reduced pressure to give a solidcrystalline material which can be recrystallized from acetonitrile,nitromethane, cyclohexane, or benzene.

In the above equation R H can be thionyl chloride or thionyl bromide aswell as HCl or HBr in order to effect the conversion of the OH group tochloro or bromo. Certain S-halogenated dihydrouracils of this inventioncan be prepared by reacting, for example, chlorine with a substituteddihydrouracial in refluxing glacial acetic acid, illustrated as follows:

n H c1 not H RiN H where R and R are defined as in Formula 1. For

further details see J. Org. Chem. 26, 1877 (1961).

Further treatment of a hy-drouracil product as shown in Equation 11 withalkaline hypochlorite in aqeuous acetic acid gives the correspondingN-chloro derivative as illustrated by the following reaction scheme:

where R R R R and R are defined as in Formula 1 with the proviso that Rand R cannot be hydrogen.

The R -hydrogen of the subject dihydrouracils can be also alkylated byconventional procedures to give those hydrouracils where R is alkyl oralkenyl. Description of typical alkylation procedures are found in Am.441, 192 (1952), and Am. Chem. J. 42, 101 (1909).

Further details regarding the preparation of dihydrouracils will befound in Journal Am. Chem. Soc., 59, 2436 (1937); Journal Am. Chem.Soc., 60, 1622 (1938);

7 Journal Biol. Chem., 199, 333 (1952); Monatsh., 64, 333

(1934); Ben, 38, 1689 (1905); Journal Org. Chem. 24, 571 (1959); and D.J. Brown, The Pyrimidines, Interscience, 1962, pp.'430445.

The hydrouracils of this invention are excellent herbicides. They areactive as agents for either preor postemergence weed control, as soilsterilants, and in soilfoliage applications. They control both annualand peren nial broadleaf weeds. and grasses such as quackgrass, Johnsongrass, crabgrass, foxtail, barnyard grass, bromegrass, broomsedge,pigweed, lambs-quarters, spurge, purslane and volunteer lespedeza. Thecompounds can also be used to control young weeds growing in establishedeconomic crops having deep root systems, without injury to these crops.Weeds such as mustard, crabgrass, velvet leaf, chickweed, flower of anhour, wild buckwheat, corn cockle, seedling cockle'bur, and seedlingJohnson grass may be controlled in crops such as corn, flax, andpeanuts.

The amounts of hydrouracils to be used in such applications willnaturally vary according to the condition of the vegetation, the degreeof herbicidal activity desired, the formulation used, the mode ofapplication, the climate, season of the year, rainfall and the like.Recommendations as to precise application rates are therefore notpractical. Generally, however, in soil-foliage applications, levels offrom 4 to 30 pounds of active material per acre will give satisfactoryresults. When these compounds are applied as preor post-emergence spraysfor the control of tender weed seedlings, rates of from /2 to 4 poundsof active ingredient per acre will be sufficient.

The compounds of Formulae, 1 and 2 can be used with a carrier or diluentsuch as a finely divided solid,

a solvent liquid of organic origin, water, a wetting agent,

a dispersing agent, an emulsifying agent, an aqueous emulsion or anysuitable combination of these.

Compositions of the invention, especially liquids and Wettable powders,contain as a conditioning agent one or more surface-active agents inamounts suflicient to render a given composition containing thecompounds of Formulae 1 and 2 readily dispersible in water or in oil. Bythe term surface-active agent," it is understood that wetting agents,dispersing agents, suspending agents and emulsifying agents areincluded. Compositions of the invention generally contain from 0.5 to99.5% by weight of one or more compounds of Formulae 1 and 2.

Suitable surface-active agents are set out, for example, in Searle US.Patent 2,426,417, Todd US. Patent 2,655,- 447, Jones US. Patent2,412,510, or Lenher,U.S. Patent 2,139,276. A detailed list of suchagents is set forth by J. W. McCutcheon, Detergents and Emulsifiersl963Annual, and Bulletin E-607 of the Bureau of Entomology and PlantQuarantine of the US. Department of Agriculture. In general, less than10 percent by weight of the surface-active agent is present in thecompositions of this invention, although usually the amount ofsurfaceactive agent in these compositions is at least 0.5 and not morethan 5 percent by weight. However, levels as high as O.5-6 parts ofsurfactant for each part of hydrouracil gives unusual and unexpectedbeneficial results. Such compositions have greater herbicidaleffectiveness than can be expected from a consideration of the activityof the components used separately.

Several different types of compositions containing the compounds ofFormulae 1 and 2 have been developed so that the compounds of Formulae 1and 2 can be used to greatest advantage as herbicides. These preferredformulations comprise certain Wettable powders, certain aqueoussuspensions, certain dusts, certain oil solutions (which may beemulsifiable in water), solutions in certain solvents, certain granulesand pellets, and certain highstrength compositions. In general, thesepreferred compositions will all usually contain a wetting agent, adispersant, or an emulsifying agent.

Wettable powders are water-dispersible compositions containing theactive material, an inert solid extender, and one or more surfactants toprovide rapid wetting and prevent heavy flocculation when suspended inwater. They are prepared by blending and grinding the ingredients untilthe particle size is less than 50 microns.

The inert extenders which should be used in the preferred Wettablepowders of this invention containing the compounds of Formulae l and 2are preferably of mineral origin and the surfactants are preferablyanionic or non-ionic.

Suitable surfactants for use in such compositions are listed inDetergents and Emulsifiers, 1963 Annual by John W. McCutcheon, Inc. Theclasses of extenders most suitable for the Wettable powder formulationsof this invention are the natural clays, diatomaceous earths, andsynthetic mineral fillers derived from silica and silicate. Organicdiluents and wood flour, walnut shell flour, and the like can also beused. Among non-ionic and anionic surfactants, those most suitable forthe preparation of the dry, Wettable products of this invention aresolid forms of compounds known to the art as wetters and dispersants.Occasionally a liquid, non-ionic compound classified primarily as anemulsifier may serve as both wetter and dispersant.

Most preferred fillers for this invention are kaolinite clay,attapulgite clay, synthetic magnesium silicate, and synthetic finesilicas. Preferred surface-active agents are alkyl benzene and alkylnaphthalene sulfonates, sulfated fatty alcohols, amines, or acid amides,long chain acid esters of sodium isethionate, esters of sodiumsulfosuccinate, sulfated or sulfonated fatty acid esters, petroleumsulfonates, sulfonated vegetable oils ditertiary acetylenic glycols.Other preferred surfactants include ethylene oxide condensates withalkylated phenols, with fatty acids, with sorbitan fatty acid esters,and with long chain aliphatic alcohols and thioalcohols. Preferreddispersants are methylated celluloses, polyvinyl alcohols, ligninsulfonates, polymeric alkyl naphthalene sulfonates, sodium naphthalenesulfonate, poly-methylene bisnaphthalenesulfonate, andsodium-N-methyl-N-(long chain acid) taurates.

Wetting and dispersing agents in these preferred wettable powdercompositions of this invention are usually present at concentrations offrom about 0.5 weight percent to 5 weight percent. The inert extenderthen completes the formulation. Where needed, a portion of the extendermay be replaced by corrosion inhibitors antitor or an anti-foaming agentor both, the corrosion inhibitor will not exceed about 1 percent of thecomposition, and the anti-foaming agent will not exceed about 0.5percent by weight of the composition, both replacing equivalent amountsof the inert extender.

Aqueous suspensions are prepared by mixing together and sandgrinding orball milling an aqueous slurry of water-insoluble active ingredient inthe presence of dispersing agents to obtain a concentrated slurry ofvery finely-divided particles, in which the active ingredient issubstantially all below 5 microns in size. The resulting concentratedaqueous suspension is characterized by its extremely small particlesize, so that when diluted and sprayed coverage is very uniform. Cakingpreventatives, such as gelling type clays, may also be included tofurther reduce the settling out of particles.

Thus, aqueous dispersions of the invention will contain from about 20 to50 weight percent active material, from 2 to 15 weight percentdispersant, from to 3 weight percent caking preventative, and from 32 to78 weight percent of water preservatives, and corrosion inhibitors canoptionally be present up to 3% of the total replacing an equivalentquantity of water.

Dusts are dense powder compositions which are intended for applicationin dry form, in accordance with the preferred compositions and methodsof the invention. Dusts are characterized by their free-flowing andrapid settling properties so that they are not readily windborne toareas where their presence is not desired. They contain primarily anactive material and a dense, freeflowing, solid extender.

Their performance is sometimes aided by the inclusion of a wettingagent, and convenience in manufacture frequently demands the inclusionof an inert, absorptive grinding aid. For the compounds of thisinvention, the inert extender may be either of vegetable or mineralorigin, the wetting agent is preferabaly anionic or non-ionic, andsuitable absorptive grinding aids are of mineral origin.

Suitable classes of inert solid extenders for use here are those organicor inorganic powders which possess high bulk density and are veryfree-flowing. They are also characterized by possessing relatively lowsurface areas and are poor in liquid absorption. Suitable classes ofgrinding aids are some natural clays, diatomaceous earths, and syntheticmineral fillers derived from silica or silicate. Among an ionic andnon-ionic wetting agents, the most suitable are the members of the groupknown to the art as wetting agents and emulsifiers as listed above.Although solid agents are usually preferred because of ease inincorporation, some liquid non-ionic agents are also suitable in thisinvention.

Preferred inert solid extenders for the dusts of this invention aremicaceous talcs, pyrophyllite, dense kaolin clays, ground calciumphosphate rock such as that known as Phosphodust (a trademark of theAmerican Agricultural Chemical Company) and tobacco dust.

Preferred grinding aids are attapulgite clay, diatomaceous silica,synthetic fine silica and synthetic calcium and magnesium silicates.Preferred wetting agents are those previously listed under wettablepowder formulations.

The inert solid extenders in the dusts of this invention are usuallypresent in concentrations of from about 30 to 90 weight percent of thetotal composition. The grinding aid will usually constitute 5 to 50weight percent of the composition, and the wetting agent will constitutefrom about 0 to 1.0 weight percent of the composition. Dust compositionscan also contain other surfactants such as dispersing agents inconcentrations of up to about 0.5 weight percent.

The wettable powders described above may also be used in the preparationof dusts. While such wettable powders could be used directly in dustform, it is more advantageous to dilute them by blending with the densedust diluent. In this manner, dispersing agents, corrosion 10inhibitors, and anti-foam agents may also be found as components of adust.

Thus, the dust compositions of this invention will comprise about 2 to20 weight percent active material, 0 to 50 weight percent absorptivefiller, 0 to 1.0 Weight percent wetting agent, and about 30 to 98 weightpercent dense, free-flowing dust diluent, as these terms are usedherein. Such dust formulations can contain, in addition, minor amountsof dispersants, corrosion inhibitors, and antifoam agents, which areoften derived from the wettable powders used to make the dusts.

Oil solution formulations are usually solutions of active material innon-water miscible solvents. If the solution is to be emulsifiable inwater, the solution also contains a surfactant.

For the compounds of this invention, oil solutions can be made by mixingthe active ingredient with a solvent, and if it is desired to have anemulsifiable oil, additionally mixing in a surfactant. Suitable solventsfor the compounds of this invention are hydrocarbons (which may bealiphatic and/ or aromatic, substituted or unsubstituted), and non-watermiscible ethers, esters, or ketones. Suitable surfactants are thoseanionic or non-ionic agents known to the art as emulsifying agents. Suchcompounds can be found listed in Detergents and Emulsifiers1963 Annual,by John W. McCutcheon, Inc.

Emulsifying agents most suitable for the compositions of this inventionare alkyl aryl polyethoxy alcohols, alkyl and akyl aryl polyetheralcohols, polyoxyethylene sorbitol or sorbitan fatty acid esters,polyethylene glycol fatty esters, fatty alkylol amide condensates, aminesalts of fatty alcohol sulfates plus long chain alcohols, oil solublesulfonates and mixtures of such materials. Such emulsifying agents willcomprise from about 1 to 10 weight percent of the total composition. Asdescribed above, however, up to 6 parts of emulsifying agent for eachpart hydrouracil can be used to give excellent herbicidal results.

Preferred solvents include hydrocarbons of the aromatic type such asxylene and heavy aromatic naphthas and ketones such as isophorone.Solvents boiling in the range of -400 C. are preferred.

Thus, emulsifiable oil compositions of the present invention willusually consist of from about 15 to 50 weight percent active material,about 40 to 83 weight percent solvent, and about 2 to 10 weight percentemulsifier, as these terms are defined and used above.

Granules or pellets are physically stable, particulate compositionscontaining active material (here, the compounds of Formulae 1 and 2)adhering to or distributed through a basic matrix of a coherent, inertcarrier with macroscopic dimensions. In order to aid leaching of activefrom the granule, a surfactant is usually present.

For the compounds of this invention, the inert carrier is preferably ofmineral origin, and the surfactant is a compound known to the art as awetting agent. Such compounds are listed by J. B. McCutcheon inDetergents and Emulsifiers-l963 Annual.

Suitable carriers are natural clays, some pyrophyllites and vermiculite.Suitable wetting agents are anionic or non-ionic.

For the granule compositions of this invention, most suitable carriersare of two types. The first are porous, absorptive, preformed granules,such as preformed and screened granular attapulgite or heat expanded,granular, screened vermiculite. On either of these, a solution or asuspension of the active agent can be sprayed and will be absorbed atconcentrations up to 25 weight percent of the total weight. The secondsuitable types are initially powdered kaolin clays, hydratedattapulgite, or bentonitic clays, either sodium, calcium, or magnesiumbentonites. These are blended with the active components to givemixtures that are granulated and dried to yield granular material withthe active component distributed uniformly throughout the mass. Suchgranules can also be made with 20 to 30 weight percent active component,but more fre- 1 1 quently a concentration of about 10 weight percent isdesired for optimum distribution. The granular compositions of thisinvention are most useful in a size range of 15 to 30 mesh.

The most suitable wetting agents for the granular compositions of thisinvention depend upon the type of granule used. When preformed granulesare sprayed with active material in liquid form, the most suitablewetting agents are non-ionic, liquid wetters miscible with the solvent.These are compounds more generally known to the art I as emulsifiers,and comprise alkyl aryl polyether alcohols,

alkyl polyether alcohols, polyoxyethylene sorbitol or sorbitan fattyacid esters, polyethylene glycol fatty esters, fatty alkylol amidecondensates and oil soluble petroleum or vegetable oil sulfonates. Suchagents will usually comprise from about 0. to 5 weight percent of thetotal composition.

When the active is first mixed with a powdered carrier and subsequentlygranulated, liquid non-ionicv wetters can still be used, but it isusually preferable to incorporate at the mixing stage one of the solid,powdered anionic wetting agents such as those previously listed for thewettable powders. Such agents will comprise from about to 2 weightpercent of the total composition.

Thus, the preferred granular formulations of this invention compriseabout 15 to 30 mesh granules containing from about to 30 Weight percentactive material, about 0 to 5 weight percent wetting agent, and about 65to 95 weight percent inert mineral carrier, as these terms are usedherein.

Pellets can be made by mixing the finely-divided uracils of thisinvention with suitable clay along with such optional ingredients asanhydrous salts, wetting agents, and dispersing agents. This mixture ismoistened with 25% by Weight of Water and is then extruded through asuitable die, under pressure. The extrusions are cut into predeterminedlengths and then dried. These pellets can be granulated if desired.

Preferred clays are of the bentonite, sub-bentonite, or

, kaolin type although a portion of these may be replaced withmontmorillonite or attapulgite when more absorptive pellets are desired.

The preferred anhydrous salt is sodium sulfate, otherwise known as saltcake, and the preferred wetting and dispersing agents are those listedabove for wettable powder formulations. These optional ingredients aidin wetting and breakup of the pellets after application.

Thus, the preferred pellet formulations of this invention will containfrom 05-30% of active material, from 5-15 of anhydrous sodium sulfate,from 0'.5-5.0% of surface active agents and from 50-94% of clay diluent.

High-strength compositions containing from 90-99.5% of active materialand 0.510.0% of a surface active agent can be prepared. The surfaceactive agent should be primarily a wetting agent but it may also havedispersing or emulsifying properties. Preferred surface active agentsare polyethylene glycol ethers of long-chain alcohols or alkylatedphenols. Preferred diluents are synthetic fine silicas, finely dividedsilicates, and finely divided clays such as kaolinite, attapulgites, andmontmorillonites. These diluent-s may serve as anti-oaking agents.

These high-strength compositions are suitable for preparation of avariety of formulations. For example, oil solutions can be prepared byaddition of the high-strength compositions to aromatic-type solvents andto herbicidal oils. Wettalble. powder, pellets, and granularcompositions can be prepared as described above with the high-strengthcomposition replacing the active in the examples.

The hydrouracils can be combined with other known herbicides to givecompositions which have advantages over the individual components. Amongthe known herbicides which can be combined with the hydrouracils areSUBSTITUTED UREAS 3 3 ,4-dichlorophenyl) -1,1-dimethylurea 3-(4-chlorophenyl) -1,1-dimethylurea 3 -phenyl-1,1-dimethylurea 3 3,4-dic-hlorophenyl) -3 -methoxy-1 1 -dimethylurea 3 4-chlorophenyl-3-methoxy-1,l-dirnethylurea 3 3 ,4-dichlorophenyl) -1-nbutyl-1-methylurea 3- 3,4-dichlorophenyl) -1-methoxy-1-methylurea 3(4-chlorop'henyl) -1-methoxy-1-methylurea 3 a 3 ,4-dichlorophenyl)-1,1,3-trirnethylurea 3-(3,4-dichlorop'henyl) -1-diethylurea 3(p-chlorophenoxyphenyl) -1, l-dirnethylurea N- 3 -trifluoromethylphenyl)-N'N-dimethylurea These ureas can be mixed with the hydrouracils inproportions of from 1:4 to 4:1, respectively, the preferred ratio being1:2 to 2: 1.

SUBSTITUTED TRIAZINES Z-chlo ro-4,6-bis (ethylamino) -'s-triazine2-chloro-4-ethylamino-6-isopropylamino-s-triazine 2-chloro-4,6-bis(methoxypropyla mino) -s-triazine 2 methoxy-4,6'bis(isopropylamino)-s-Itriazine Z-diethylarnino-4-isopropylacetamido-6-methoxy-striazine2-isopropylarnino-4-methoxyethylamino-6 methylmercapto-s-triazine2,4-bis- (3 -rne-thoxypropylamino) -6+methylmerc-apto-striazine2-methylmercapto-4,6-bis(isopropylamino-s-triazine2-methylmercapto-4,6-bis ethylamino) -s-triazine2-methylmeroapto-4-ethylamino-6-iso propylamino-striazine2-methoxy-4,6-bis- (ethylamino) -s-triazine2-methoxy-4sethylamino-6-isopropylamino-s-triazine 2-chloro-4,6-bis(isopropylamino) -s-triazine These triazines can be mixed with thehydrouracils in proportions of from 1:4 to 4:1, respectively, thepreferred ratio being 1:2 to 2:1.

PHENOLS Dinitro-o-sec-butylphenol and its salts Pentachlorophenol andits salts These phenols can be mixed with the hydrouracils inproportions of 1:10 to 20:1, respectively, the preferred ratio being 1:5to 5:1.

CARBoxYL'Ic ACIDS AND DERIVATIVES The following carboxylic acids andderivatives can be mixed with the hydrouracils in the listedproportions: 2,3,6-trichlorobenzoic acid and its salts 2,3,5,6-tetrachlorobenzoic acid and its salts2-methoxy-3,5,6-trichlor0benzoic acid and its salts2-rnethoxy-3,6-dichlorobenzoic acid and its salts3-amino-2,5-dichlorobenzoic acid and. its salts3.-nitro-2,5-dichlorobenzoic acid and. its salts2,4-dichlorophenoxyacetic acid and its salts and esters2,4,S-trichlorophenoxyacetic acid and its saltsand esters(2-methyl-4-chlorophenoxy) acetic acid and its salts. and

esters 2-methyl-3,6-dichlorobenzoic acid and its salts 2,3,6-tricblorobenzyloxypropanol 2-(2,4,5-trichlorophenoxy)propionic acidand its salts and esters 2- 2,4,5 :trichlorophenoxy)ethyl-2,Z-dichloropropionate 4-(2,4-dichlorophenoxy)butyric acid and itssalts and esters 4(2-methyl-4-chlorophenoxy)butyric acid and its saltsand esters Mixed in a 1:16 to 8:1 ratio, preferably a 1:4 to 4:1 ratio.

2,6-dichlorobenzonitrile: Mixed in a 1:4 to 4:1 ratio, preferably a 1:3to 3: 1 ratio.

Trichloroacetic acid and its salts: Mixed in a 1:2 to 25:1 ratio,preferably a 1:1 to 8:1 ratio.

2,2-dichloropropionic acid and its salts: Mixed in a 1:4 to 8:1 ratio,preferably a 1:2 to 4:1 ratio:

N',N-di(n-propy1)thiolcarbamic acid, ethyl ester; N,N-di(n-propyl)thiolcarbamic acid, n-propyl ester; N-ethyl- 13N-(n-butyDthiolcarbamic acid, ethyl ester;N-ethyl-N-(nbutyl)thiolcarbamic acid, n-propyl ester: Mixed in a 1:2 to24:1 ratio, preferably a 1:1 to 12:1 ratio.

N-phenylcarbamic acid, isopropyl ester; N-(m-chloro- 1 4-br0mo-3-isopropyl-6-methyluracil and salts5-chloro-3-ispropyl-6-methyluralcil and salts5-brorno-3-sec-butyl-6-methyluracil and salts3-sec-butyl-S-chloro-6-methyluracil and salts phenyl)carbamic acid,isopropyl ester; N-(m-chloro- 5 5-bromo-3-cyclohexyl-6-methyluracil andsalts phenyl)carbamic acid, 4-chloro-2-butynyl ester: Mixed5-chloro-3-cyclohexyl-6-methyluracil and salts in a 1:2 to 24:1 ratio,preferably a 1:1 to 12:1 ratio. 5-bromo-3-tert-butyl-G-methyluracil2,3,6-trichlorophenylacetic acid and its salts: Mixed in3-tert-butyl-5-chloro-6-methyluracil a 1:12 to 8:1 ratio, preferably a1:4 to 4:1 ratio. f 1 1.21;

2 chloro N,N diallylacetamide; maleic hydrazide: 10 Mixed m a to ra preerab y a o m Mixed in a 1:2 to 10:1 ratio, preferably a 1:1 to 5:1ratio. 3-cycloheXyl-6-methylllracll I M I O S 3-cyclohexyl-6-ethyluracilNORGANIC AND IXED NORGANIC- RGANIC ALTS g c buty1 3 c1 0h exylur a CHThese salts can be mixed with the hydrouracils in the3-cyclohexyl-6propyluracil listed proportions.3-cyclopentyl-6-rnethyluracil Calcmm propylarsonate. dlsodmmmonometilylarso' Mixed in a 1:4 to 4:1 ratio, preferably a 1:2 to 2:1ratio. nate, octyl-dodecylammoniummethylarsonate, dimethyld t 41 f M3-cyclohexyl-5,6-tr1methyleneurac1l i :f lxe m a O Ta pre era y a3-sec-butyl-5,6-trimethyleneuracil 3-isopropyl-5,6-trimethyleneuracilabifgllllij taO1'?2'65n'1;61:a%\i [01X6d in a 1.5 to 40.1 ratio, prefer3 isopmpyl s,6 tetramethyleneuracil Lead iarsenate, calcium arsenate:Mixed in a 150:1 to 3-1801) mp yl-56 p entamethyleneuracli 600:1 ratio,preferably a 100:1 to 400:1 ratio. Mixed in a 1:6 to 6:1 ratio,preferably a 1:4 to 4:1 ratio.

Sodium tetraborate hydrated, granulated, sodium meta- 5 bmmoycwlohewluracil borate, sodium pentaborate, polyborchlorate, unrefined 5chlOrO 3 cyclohexyluracil borate ore such as borascu: Mixed in a 3:1 to120:1 5 brOmO 3 isopmpyluracfl ratio, preferably a 6:1 to 60:1 ratio. II 5 bromo 3 Sec buty1uraci1 Ammonium thiocyanate. Mixed in a 1.10 to20.1 ratio, 3 sec buty1 5 ch1omuraci1 preferably a 1:5 to 5 :1 ratio.

Sodium chlorate: Mixed in a 1:1 to 40:1 ratio, prefer- MlXed 111 a 136to 611 a Preferably a 112 to 211 ratloy a 211 to 2011 Tatio- IS-bromo-3-isopropyl-6-methyl-l-trichloromethylthio- Ammonium sulfamate:Mixed in a 1:1 to 100:1 ratlo, uracil Preferably a 151 to 50:1 ratio-5-brorno-3-cyclohexyl-6-methyl-l-trichloromethylthio- OTHER ORGANICHERBICIDES uracil 5,6 dihydro (4A,6A) dipyrido (1,2-A,2,1'-C), i' il'g'g 'gf fi g f fl pyraziniurn dibromide: Mixed in a 1:20 to 16:1ratio, g y 'i g fiz i z mac th preferablya 1:5 to 5:1 ratio. 'lsopropy yme (Home y louracl 3-amino-1,2,4-triazole: Mixed in a 1:20 to 20:1ratio, mixed in a 1:4 to 4:1 ratio, preferably a 1:2 to 2:1 ratio.preferablya1:5to5z1ratio. 40 This invention will be more easilyunderstood and 3,G-endoxohexahydrophthalic acid: Mixed in a 1:3 toreadily practiced by referring to the following illustrative 20:1 ratio,preferably a 1:2 to 10:1 ratio. examples: Hexachloroacetone: Mixed in a1:2 to 16:1 ratio, pref- EXAMPLE 1 erablya1z1to8z1ratio.Diphenylacetonitrile, N,N-dimethyl a,a diphenyl- Prepalanon of gjsg zgziiig iff 6meth0xy' acetamide, N,N di n propyl 2,6 dinitro 4trifiuorornethylaniline, N,N di n propyl 2,6 dinitro- A mixture of 192parts of 3-sec-butyl-6-methyluracil 4-methylaniline: Mixed in a 1:10 to30:1 ratio, prefera 1000 pa f m t anol is tirr d beneath a nitroablya1:5 to 20:1 ratio. gerli1 blacrilCllmt1 aa h 142 pagts of gaseouschlorine are gad- O (2,4 dichlorophenyl) O methyl isopropylua y a e eexot errmc reaction is maintarne at phosphoramidothiate, 2,3,5,6tetrachloroterephthalic With a cooling bath- The addition f the 1 acid,dimethyl ester: Mixed in a 1:4 to 20:1 ratio, prefn 18 completed inabout 1 hour, and the reaction ixerably a 1:3 to 15;1rati ture isstirred at 25 C. for an additional 2 hours.

2,4 dichloro 4' nitrodiphenyl th r; Mi d i a The resulting slurry isconcentrated at reduced presl:10 to 30:1 ratio, preferably a 1:5 to 20:1ratio. sure to about one-third of its original volume, chilled OTHERSTTTTTTUTTT UTTCTLS 2- 220353512?-5323133216fiiyiifi iiii fiiliuiitfijThe hydrouracils can also be combined With other M.P. 144 C. to 147 C.is sufiiciently pureforformulasubstituted uracils, in the proportionslisted below. tion as an herbicide. Methods for the preparation of thelisted uracils which The compounds in the following table are preparedare novel can be found in Patents Nos. 3,245,357, issued in a similarfashion by substituting the listed reactants Feb. 15, 1966, and3,235,360, issued Feb. 15, 1966. for those specified above.

Substituted Uracil Parts by Alcohol Halogen Parts by SubstitutedHydrouracll Product weight weight 3-propyL6-methyluraei1 168 Methano1Ch10rine 142 5,5-dichloro-6-methoxy-fi-methyl-3-propylhydrouracil.3-isopropyl-6-methyluraci1 168 do 1426,5-dichlor0-6-methoxy-B-methyl-3-isopropylhydrouracil.

Do 168 Isopropanl 1425,5-dichl0ro-6-is0propoxy-dmethyl-3isopropylhydrouracil.6,6-dimethyl-3-1sopropylura 182 Methanol 715-chlor0-6,6-dimethyl-fi-methoxy-3-isopropylhydrouraeil. Do 182 d5-br0m0-5,6-dimethyl-6-methoxy-3-isopropylhydrouracil.

3-isopropyl-G-methyluracil. 168

3-isopropyl-G-ethyluracil 182 Methanol do..3-isopropyl-5-ethy1-6-methyluracil.. 196 do do.....

3-isopropy1-6methyl-5-nitrouracil. 213 do .do

3-isopropyl-5-methoxy-6- 198 do do methyluracil.

142 6,fi-dichloro-fi-ethyl-6-methoxy-3-isopropylhydrouracil.

71 5-chloro-5-ethyl-fi-methoxy-G-methyl-3-isopropylhydroura- 1 7 EXAMPLE2 Preparation of 3-sec-butyl5,6-trimethylenehya'rouracil A mixture of208 parts of 3-sec-butyl-5,-trimethyleneuracil, 18.5 parts of 5%ruthenium on carbon and 7300 18 During the course of the reaction, theoriginal solid dissolves completely and a new solid reprecipitates. Thisis filtered 01f, washed with cyclohexane and dried. The product issufliciently pure for incorporation into herbicidal formulations.

parts of dioxane is charged into an autoclave and shaken 5 The followingcompounds are prepared in a like fashin hydrogen at a pressure of 1000psi. and a temperion by substituting the listed reactants for those usedin ature of 200 C. for 3 hours. The reaction mixture is this example.

Uracil Starting Material Parts by Halogen Parts by Anhydride HydrouracilProduct weight weight 5,6-dimethyl-3-isopropyluracil 182 Chlorine. 71Araeti; anhyfi-acetoxy-5-chloro-5,G-dimethyl-3-isopropylhydrouracil.

T1 6. 3-isobutyl-6-rnethyluraeil 182 do6'acetoxy-3-isobutyl-5,Erdichloro-fi-methylhydrouracil.5-chloro-3-isopropyl-G-methyluracil 202. 5 Brominefi-acetoxy-5-bromo-5-chloro-3-isopropyl-G-methylhydrouracil.3-5ec-butyl-fi-methyluraeil 1826-acetoxy-3-see-buty1-5,5-diehloro-fi'methylhydrouraell.3-5ec-amyl-6-rnethyl-5-nitrouracil. 241 fi-acetoxy-3-Sec-amyl-5-hloro-G-methyl-5-nitrohydrourae11. 3-cyclopentyl-6methyluracil 1946-acetoxy-3-cyclopentyl-5,5-dichloro-fi-methylhydrouracil.3cyclohexyl-G-methyluracil 108 142 .do6-acetoxy-3-cyclohexyl-5,5diehloro-6-methylhydrouracil.3-1s0propyl-6-methyluracil 168 142 Plgftpopc an-5,5-diel-iloro-3-isopropyl-B-methyl-fi propionoxyhydroy n e. urae1. Do168 142 Chloroacetic6-ch1oroacetoxy-5,5-dich1oro-fi-methyl-B-isopropylhydroanhydride.uracil. 3-eyelooctyl-6-methylnracil 236 142 Agetiz anhy-6'acetoxy-3-cyclooctyl-5,5-dichloro6-methylhydrourac11.

11 6. 3-eyelohexyl-5-methoxymethyl-S- 252 71 dofi-acetoxy-5-ehloro-3-eyclohexyl-5-methoxymethyl-6- methyluracil.methylhydrouracil. 6-chloro-3-propyluracil 188.56-acetoxy-3-isopropy1-5,5,G-trlchlorohydrouractl.3-butyl-6-methoxyuraciL 1986-acet0xy-3-butyl-5,5-dichloro-G-methoxyhydrouracrl.3-terhbutyl-G-methyluracil 182 d 1 d 6butyroxy-3-tertbutyl-5,5-dichloro-fi-methylhydlollracllrryi e.5-fiuoro-B-methyl-S-phenylnracil 220 Bromine 160 Agata; anhy-6-acetoxy-5-bromo-5-fiuoro-6methy1-3-phenylhydrourac1l.

n e. 3-cyelohexyl-5,fi-dirnethylnraeil 222 Chlorine 71 do6-aeetoxy-5-chloro-3-eyelohexyl-5,ddimethylhydronracil.3sec-buty1-6methyluracil 182 o 142 flillxaglqgi an-8-sec-butyl-5,5-dichloro-G-haxanooxy-G-methyluracil. y n e.6-methyl-3-phenyluraeil 202 .do 142 Artzietiz anhy-G-aeetoxy-S,5-dichloro-6-methyl-3-pl1enylhydr0u1ac1l.

filtered free of suspended catalyst while hot, and the EXAMPLE 4resulting solut1on.1s concentrated to about one-tenth of Preparation of3 l-S0pr0pyl 64W!y[ 556 tric.hl0m its volume at reduced pressure.hydmunyil The solution is cooled, and the solid which precipitates isfiltered olf and recrystallized from acetonitrile. The Into a Vessel qpp Wlth Stlffel'. y- C011- resulting white, solid3-sec-butyl-5,6-trimethylenehydrouracil melts at 131-134 C.

The compounds in the following table are similarly prepared bysubstituting the listed uracil starting matedenser, and thermometer areplaced 500 parts of acetic acid, 200 parts of water and 168 parts of3-isopropyl-6- methyluracil. The mixture is stirred and maintained at30-35 C. as 147 parts of chlorine are gradually added.

rial for 3-sec-butyl-5,6-tnmethyleneurac1l. The reaction is rapid andafter the mixture has been Uracil Starting Material Parts By HydrouracilProduct Weight 5,G-dimethyl-S-butyluracil 1965,6-dimethyl-3-butylhydrouracil. 5,6-dlmethyl-3-secbutyluraeil 1965,6-dimethyl-3-sec-butyll1ydrouracll. 5,6-dirnethyl-3'(2-meth ylbutyl)uracil 210 5,6-din1ethyl-3-(2n1ethylbutyl)hydrouracil.5,6-dimethy13-pentyluracil 210 5,6-dimethyl-3-pentylhydrouracil.3-cyclohexy ,fi-dimethyluraeil 224 3eyclohexyl-5,6-dimethylhydrouracll.5,6dimethyl-3-isopr0pylnracil 182 5,fi-dimethyl-B-isopropylhydrouracxl.3-(2-methylbutyl)-5,6-trimethyleneuracil 2223-(2-methylbutyl)-5,G-trimethylenehydrouracfl.8-cyclohexyl-5,Gtrimethyleneuracil 2363-cye1ohexyl-5,fi-trimethylenehydrouracrl.3-is0propyl-5,G-tetramethyleneuracil. 2083-isopropy1-5,G-tetramethylenehydrouraeil3-eyc10hexyl-5,6-tetramethy1eneuracil 2503-eyelohexy1-5,6-tetramethylenehydronracil. fimethyl-3-phenyl-5-propy1uracil 2446-methyl-3-phenyl-5-propylhydrourac1l. 5-butyl-3-phenyluracil 2435-butyl-8-phenylhydrouracil. I 3-sec-butyl-5,G-tetramethyleneuraciL 2223-sec-butyl-5,fi-tetramethylenehydrouraml.3-isopr0pyl-5,fi-pentamethyleneuraciL. 2223-isopr0pyl-5,fi-pentamethylenehydrouraeil.6-ethyl-3-isopropyl-5anethyluracil 1966-ethyl-3-isopropyl-dmethylhydrouractl 3- v h v -fi t yl-fi-methyluracil238 3cyelohexyl-6-ethyl-5-methylhydrourac1l. yd oxymthy1-3-isopropyl-G-methyluracil 1865-hydroxymethyl-B-isopropyl-S-methylhydrouracil.3-5ec'hutyl-5-hydroxymethyl-G-methyluracil 2003-see-buty1-5-hydroxymethyl-fi-methylhydrouraclh3-0yclohexyLfi-methoxyrnethyl-fi-methyluraciL 2383-cyclohexyl-S-methcxymethyl-fi-methylhydrouraeil.B-isopropy1-5-methoxymethyl-fi-methyluracil 1983-isopropy1-5-methoxymethyl-fi-methylhydrouracll.3-(3a,4,5,6,7,7a-hexahydro4,7-methano-5-indeny1)-5,6-trimethyl- 2993-(3a,4,5,6,7,7a-hexahydro-4,7-methano-5-mdenyl)-5,6-tr1methyleneeneuracil.hydrouraeil. 3-(bicy01o[3,2,1]oct-3-yl)-6-methyluracil 2483-(bicyclo[3,2 lloct-S-yl)-6-methy1hydrourac1l.3-cyclopropyl-5,fi-dimethyluracil 180 3'eyclopropy-5,6-dimethylhydr0urac1l.3-(decahydro-l,4,5,8-dimethanonaphthy1methyl)-6-n1ethyl- 2993-(decafilydro-l,4,5,8-dimethanonaphthylmethyl)-6 methylhydrouraci. uracEXAMPLE 3 stirred for a short time, an additional 800 parts of water areadded Preparation of 6-acetoxy-5,5-dzchl0r0-3-is0pr0pyl-6- te ed off.The methylhydroumcll The resulting SOlld white precipitate is fil r Amixture of 168 parts of 3-isopropyl-6-methyluracil and 1000 parts ofacetic anhydride is maintained under a nitrogen blanket with stirring,as 142 parts of gaseous chlorine are gradually added. The reactionmixture is maintained at 10 C. with a cooling bath. The addition ofchlorine is complete in about 1 hour and the reaction is stirred at wetice-bath temperature for an additional one-half hour.

filter cake is resuspended in 600 parts of water, filtered, and thesolid allowed to air dry. The 5,5-dichloro-6-hydroxy-3-isopropyl-6-methylhydrouracil thus prepared 7 melts at1365-1385 C.

Five hundred parts of thionyl chloride are placed in a vessel equippedWith a stirrer and a condenser fitted with a scrubber to wash awaycorrosive gases. To this are gradually added, with stirring, 255 partsof the 5,5-dichloro 6-hydroxy-3-isopropyl-6-methylhydrouracil. Stirringis continued until hydrogen chloride and sulfur dioxides evolutionceases.

A total of 800 parts of cyclohexane mixture and the resulting whitesolid tered off. The precipitate is resuspended in 400 parts ofcyclohexane and refiltered. The solid is dried in a vacuum oven at roomtemperature. The subject product is sufliciently pure for incorporationinto herbicidal formulations.

The compounds listed in the following table are prepared in a similarfashion by substituting the listed reactants for those used in thisexample.

hydrouracil are added to the precipitate is filhydrouracil hydrouracil5-butylthio-5-chloro-6-ethoxy-3-isopr0pyl-6-methyl- 5-chloro-6-ethoxy-5-fluromethyl-3-isopropyl-6-methyl-S-chloro-6-ethoxy-3-isopropyl-5-methy1-6-methylthio- 5 -chloro-3cycloheXyl-6-ethoxy-6-methyl-5 -methylthiomethlyhydrouracilS-amyloxymethyl-S-chloro-6-methyl-3-phenylhydrouracil HydrouracilProduct 5 ,6-dichloro-3-isopropyl-5 ,6-trimethylenehydrouracil5,6-dichloro-3-isopropyl-G-methyl-S-nitrohydrouracil3'butyI-FrmethyI-E,5,6-trichlor0hydr0urae1l.(i-methyl-B-see-butyl-S,5,ii-triehlorohydrouracil3-cyclohexyl-6-methyl-5,5,fi-trichlorohydrouracil.6-methyl-3-pentyl-5,5,6trichlorohydrouracil.

3'cyclo0ctyl-6methyl-5,5,6-trichlorohydrourac1h6-ethyl-3-isopropy1-5,5,6-triohl0r0hydr0uraeil3-cyclohexyl-6-ethyl-5,5,6tr1chl0rohydrouracil.3-isopropy1-5,5,6,G-tetrachlorohydrouracil.6-methy-3-phenyl-5,5,(i-trichlorohydrouracu.6-ethyl-3-phenyl-5,5,6trichlor0hydrouracil.6-methyl-3-p-tolyl-5,5,Mriehlorohydrouraoil.

3-cyclopentyl-6-methyl-5 5 fi-trichlorohydrouracil.3-cycloheptyl-dmethyl-5:5:fi-trichlorohydrouraeil.

3-(p-chlorophenyl)-6-methyl-5,5,Q-trichlorohydrouracil.6-methyl-3-p-nitrophenyl-5,5,fi-trlchlorohydrouraeil.

The compounds listed in the following table can also be prepared by theforegoing methods:

6-cyclohexyloxy-3 -isopropyl-5 ,5 ,6-trichlorohydrouracil5-bromo-5-chlor0-3 -cyc1ohexyl-fi-ethoxy-o-methylhydrouracil5,6-dichl0ro-S-hydroxymethyl-G-methoxy3- (4-methyl-3-nitrophenyl)hydrouracil 5 ,5 -dichloro-3- (2,6-dinitrophenyl)-6-ethoxy-6-ethylhydrouracil3-sec-butyl-5,5-dichloro-6-methoxyhydrouracilS-bromo-6-bromomethyl-6-ethoxy-5-nitro-3-phenylhydrouracilS-bromo-S-chloro-6-cyclohexyloxy-6-methyl-3-phenylhydrouracil-5-bromo-6-chloro-3-cyclohexyl-6-methoxy-5 -nitrohydrouracil5,5-dichloro-6-ethoxy-6-methyl-3-(m-trifluoromethylphenyl)hydrouracil5,5 -dichloro-6-ethoxy-6-methyl-3-( m-perchlorylphenyl) hydrouracil5chloro-3-cyclohexyl-5- (S-hydroxyamyl 6-methoxy-6- uracil 3O5,6-dichloro-6-ethyl-5-methoxymethyl-3-phenylhydro- 3- 2,5-dimethylcyclohexyl) -6ethyl-5-methylhydrouracil5,6-dimethyl-3-(2,4-dimethylcyclohexyl)hydrouracil 3- (2,5-dimethylcyclohexyl)-5 ,G-trimethylenehydrouracil3-cyclooctyl-S,6-pentamethylenehydrouracil EXAMPLE 5 Preparation of3-methylhydrouracil A solution of 117 parts of ethyl fi-aminopropionatein 500 parts of dioxane is treated with 57 parts of methyl isocyanate.The temperature during this addition is maintained at -30 C. by externalcooling. The solution is stirred minutes longer; after which the solventis stripped under reduced pressure. The residue is then mixed with 300parts of 6 N hydrochloric acid and refluxed for 3 hours. Evaporation todryness then gives 3- methylhydrouracil which may be purified byrecrystallization from alcohol, M.P. 1295-131 C.

The compounds listed in the following table are prepared in similarfashion by substituting equimolar amounts of the reactants listed forthe ethyl fi-aminopromethylhydrouracil pionate and methyl isocyanateused in the example.

yauate i -amino Ester Hydrouracil Product Cyclohexylisocyanate EthylB-amino-fi-rnethylbutyrate 3-cyclol1exyl-6,(idimethylhydrouracil.

Norboruylmethyl isocyanate secbutyl isocyanate Phenyl isocyanateNaphthyl isocyanate (2-cyanoethyl) isoeya-nate l Dibromonorhornylisocyanate Qyclooctyl isocyanate tert-butyl isocyanate m-Chlorophenylisocyanate m-Bromophenyl isocyanate 2,4,5-trichloropheuyl isocyanateChloroethyl isocyanate a-Furfuryl isocyanate Ghlorocyclopropylisocyanate Diehlorodecahydro-l,4,5,8dimethanonaphthyl isocyanate.

Cyclobutenyl isocyanate Octahydro-l,4,5,8-dimethanonaphthyl isocyanate.

Cyclobutenylmethyl isocyanate tOctahydro-l,4,5,8-dimethanonaphthylmethyl isocyanate.

Dibromodecahydro-l,4,5,8 dimethanonaphthylmethyl isocyanate.

2,3-dichlorocyclobuty1methyl isocyanate 2methoxy-l-cyclobutenylmethylisocyanate Chlorooctahydro-l,4,5,S-decahydronaphthylethyl isocyanate;

Ethyl B-amiuobutyrate Ethyl fl-aminooctanoate Ethylfi-amino-m,a-B-trimethylbutyrate Ethyl B-amino-cr-butylpropionate Ethylfl-amin0-ycl1lorobutyrate Ethyl B-amino-a,wdimethylbutyrate EthylB-aminopl'opionate Ethyl B-amino-a-fluorobutyrate Ethyld-aminofl-methylbutyrate Ethyl fi-am1l1o-xethylp1'0pionate EthylB-amino-y-bromoheptanoate. Ethyl {i-amino-a-methylthiobutyrate Ethylfi-amino-a-butylthiopropionate r Ethyl fl-amino-a-methylpropionate EthylB-ammo-a-methylthiomethylbutyrato Ethylfi-methylamino-a-methoxypropionate.

Ethyl B-amino-a-hydroxypropylbutyrate t Ethyl B-amino-a-propoxyvalerateEthyl [:l-aminobutyrate Ethyl fi-amino-a-ehlorobutyrate r Ethylfi-amino-a-iodopropionate i 3-norbornyhnethyl-6-methylhydrouracil.3-sec-butyl-G-amylhydrouracil. 3-pheny1-5,5,6,dtetramethylhydrouracil.3-a-napthhyl-S-butylhydrouracil.3-(2-cyauoethyl)-6-cl1lor0methylhydrouracil.3-(dibromonorbornyl)-5,5,G-trimethylhydrouraeil3-cyclooctylhyclrouracil. 3-tertbutyl-5 flu0ro-tlmethylhydrouracil.3-m-chl0rophenyl-5,B-dimethylhydrouracil.3-m-brom0phenyl-5,(idirnethylhydrouracil.5,Gdimethyl-3-(2A,fi-ti'ichlorophenyl)hydrouracil3-chloroethyl-5-ethylhydrouracil.3-(a-furfuryl)-6-bromobutylhydrouvacil.3-chlorocyclopropyl-G-methyl-5-methylthiohydrouracil.3-(dichlorodecahydrod,4,5,8-dimethano naplithyl)-5-butylthiohydrouracil.3-cyol0butenyI-S-methylhydrouracil.3-(octahydro-l,4,5,8-dimethanonaphthyl)-6-methyl-5methylthiomethylhydrouracil.3-cyclobuteuylmethyl-fi-rnethoxy-l-methylhydrouracil. 3-(octahydro-Li,5,8-dimethanonaphthyl)-5- methyl-5-hydroxypropylhyclrouracil.3-(dibromodecahydro-1,4,5,8-dimethano-naphthylmethyl)-6-ethyl5propoxyhydrouracil.3-(2,3-dichlol'ocyclobutylmethyl)-6 methylhydrouracil.3-(2methoxy-l-cyelobutenylmethyl)-5-eh10ro-6- methylhydrouracil.3-(ohlorooctahydro-l,4,5,8-decahydronaphthylethyl)-5iodohydrnuraeil.

21 EXAMPLE 6 Preparation of 3-butyl-fi-methylhydrouracil An intimatemixture of 40 parts of erotonic acid and '5 8 parts of butylurea isheated at 210-220 C. for 2 hours. The liquid is then cooled and theresulting glassy solid recrystallized to give pure3-butyl-fi-methylhydrouracil.

The compounds listed in the following table are prepared similarly bysubstituting equimolar amounts of the reactants listed for the crotonicacid and butylurea used dried again. The resulting essentially pure1,3-diisopropy1- 5,6-trimethylenehydrouracil can be used as such orrecrystallized from a suitable solvent if higher purity is desired. I

Other l-alkyl, alkenyl, etc., hydrouracils listed below can be preparedin a similar fashion 'by substituting equivalent amounts of theappropriate alkyl halide and hydrouracil for the isopropyl bromide and3-isopropyl-5,6-trimethylenehydrouracil.

1n the example. 10 l-allyl-3-sec=butyl-6-methyl-5 -n1trohydrourac11Substituted Urea afi-unsatiflated Acid Hydrouracil ProductCyclopentenylurea. afi-Dimethylcromuic acid3-cyclopentenyl-5,Sfi-trimethylhydrouraeil. Decylurea HcptQ-enoic acid3-decyl-6-buty1hydrouracil. Tetrahydroiuriurylurca a-E thylacrylic acid3-tetrahydrofuriuryl-5-ethhlhydr0uracil. 2,fi-diisopropylbenzylureaa-Methylcrotonic acid 3-(2,(Hliisopropylbenzyl)-5,odimethylhydrouracil.Oct-3-ynylurea Crotonic acid 3-(oct-3-ynyl)-6-methylhydrouracil.Oyclohexylurea Methacrylic acid 3-cyclohexyl-5-methylhydrouraeil.Cyclobutenylurea a-S-DimethyIpenten-QrOiO aci3-cyclobutenyl-(rethyl-5,fi-dimethylhydrouracil. Propynylureaa-Methylcrotonic acid 5,6-di1nethyl-3-propyuylhydrouracil. m-PyridylureaMethacrylic acid 5-methyl-S-m-pyridylhydrouracil. Mcthylurea;a-Methylcrotonic acid. 3,5,G-trimethylhydrouracil. a-NaphthylmethylureaMethacrylic acid. 5-methyl-3-a-naphthylmethylhydrouracil.fi-nitroiuriurylurea 5-methyl-3-(5-nitrofuriuryl) hydrouracil.(2-buten-2-yl) urea 3-(2-buten-2-yl)-5 methylhydrouracil.

S-cyanopentylurea 1,1,5-trimethy1-S-hydroxypentylurea 5methoxycarbonylpentylurea Ethoxycarbonylmethylurea 2-hydroxyethylurea1,2-dimethylcyc1opentylurea 6-methoxy-3,3-dimethylindanylurea3-a-myloxypropylurea Decahydro-l ,4,5,8-dimethynonaphthylurea..

3-(5-cyauopeutyl)-5-6-dimethylhydrouracil.5,6dimethyl-3-(1,1,5-trimethyl 5-hydroxypentyl) hydrouracil. 5,(rdin11ethyl-3-(5 methoxycarbonylpentyl)hydrouracr5,[idimethyl-3-(ethoxycarbonylmethyl)hydrouracil.5,6-dimethyl-3-(Z-hydroxyethyl)hydrouracil.5,6-dimethyl-3-(1,2-dimethylcyclopentyl)hydrouracil.5-mcthyl-3-(6-meth0xy-3,S-dimethylindanyl)hydrouraci.3-(2-bromoethyl)-5-ethylhydrouracil. 5-ethyl-3-(octen-7-yl)hydrouracil.5-ethyl-3-(m-trifiuoromethylphenyl)hydrouracil.3-(x-chloronorbornybhydrouracil.3-(o-fluorophenyl)-5-rnethy1hydrouracil.3-(2-meth0xyethyl)-5-mcthylhydrouracil.3-(carvacryl)-5-metl1ylhydrouracil. r5-rnethyl-3-(4-methoxycyclohexen-l-ylmethyl)hydrouracil.3-(4-chlorobutyl)-5-methylhydrouracil.3-(o-biphenylyl)-5-methylhydrouracil.3-(3methoxypropyl)-5-methylhydrouraicl.3-(2,3-dibromobutyl)-5-methyl.hydrouracil.3-(3-amyloxypropyl)-5-methylhydrouracil.3-(decahydro-l,4,5,8-dimethyuonaphthyl)hydrouraci EXAMPLE 8 Preparationof 1,3-diispropyl 5,6-trimethylenehydrouracil A suspension of the sodiumderivative of 3-isopropyl- 1ethyl-3-see-butyl-5,ddimethylhydrouracil 1-(4-chlorobutyl -5, 6-diethy1-3-phenylhydrouracil 1 -2-hydroxyethyl -3-cyclohexylmethyl- -methylhydrouracil 1- 3 -ethoxypropyl -3 ethyl-5,o-dimethylhydrouracil 5,6-trimethylenehydrouracil in dioxane isprepared, under 1-(Z-cyanoethyl)-3-tert-butyl-6-methylhydrouracilanhydrous conditions and in an atmosphere of nitrogen,1-3-methoxycarbonylpfopyl)-3-n-pentylhydrouracil by the gradualadditionof 48 parts by weight of sodium 1-(2-carboXyethyl)-3-sec-buty1-5,6-dimethylhydrouracil hdri9d6e(55%bactive i2 milegral oil) tolag s6tirred SghiltiOn E L 9 o 1 arts yWeig t o -isopropy -trimet y enchydrour cil in 1000 parts by weight ofdioxane. Forma- Prepamnon of 5 bmmo 3 ,cyclohexilhydfomc" tion of thesodium derivative is accompanied by the total f 'I of bromme contamed ofevolution of hydrogen glacial acetic acid is added dropwise to a wellstirred and When hydrogen evolution ceases, the sodium salt susrefluxingsiolunon of 5 of CV61? hexylhydliouracfl pension is heated to reflux andStirred as 123 parts by contained in 60 ml. of glacial acetioa-cid.Approximately weight of siopmpyl bromide are gradually added 1/2 hoursare required for the addition. The solution is timing is continued untilsodium bromide formation 9 ,whereu'pon f i It Is collected and ceasescrystallized from acetorntrile to give pure 5-bromo-3-cyclo- Aftercooling, the mixture'is cautiously dilutedwith hexylhydrouracfl.melting2 7 water to precipitate the product, which is filtered, dried, 'Ijheprodllcts h a are Prepared m washed with cold heptane to remove mineraloil, and 0 s milar fashion by substituting equivalent amounts of thelisted reactants for those specified above.

Dihydrouracil Reactant Halogen I Hydrouracil Product8-sec-butyl-fi-methylhydrouracil Bromine5-bromo-3-sec-butyl-6-methy1hydrouracil.

3-tert-butyl-S-rnethylhydrouracil. 3-(1-ethylpropyl)-8-methy1hyrouracil.. 3-cyclohexylmethyl-G-methylhydrouracil..3-cyclohexylmethyl-fi-methylhydrouracil. 3-phenyl-6-methylhydrouracil3-sec-butyl-B-methylhydrouracil 3-isopropy1-fi-methylhydrouracil.3-norbornylmethyl-G-methylhydrouracil B-sec-butyl-fi-methylhydrouracil3-cyclohexyl-5-methylhydrouracil. 3-eyclohexyl-5-methoxyhydrouraei1Chlorine. Bromine.

Chlorine.

5-hromo-3-tert-butyl-fi-methylhydrouracil.5-bromo-3-(l-ethylpropyl)-6-methylhydrouracil.5-bromo-3-cyclohexlmethyl-G-methylhydrouracil.5-chloro-3-cyc1ohexylmethyl-G-methylhydrouracil.5-bromo-fi-methyl-3-phenylhydrouracil.5-ch1oro-6-methyl-3sec-butylhydrouraeil.5-br0mo'3-isopropyl-fi-methylhydrouracil.5-br0mo-6-methyl-3-norbornylhydrouracil.

5-chloro-3-sec-butyl-5-methylhydrouracil.

5-bromo3-cyclohexyl-5-methylhydrouracil.5-chloro-3-cyclohexyl-5-methoxyhydrouraeil.

1 5 ,5 -dichloro-3,6 dimethyl-6-methoxyhydrouracil 1 23 EXAMPLE 10Preparation of 6-meth0xy-6-methyl-3-is0pr0pyl-1,5,5-trichlorohydrouracilA total of 26.9 parts by weight of 5,5-dichloro-6-methoxy-6-methyl-3-isopropylhydrouracil is combined with 200 parts byweight of acetic acid and 40 parts by weight of water. This mixture iscooled to C. and stirred while a cold aqueous solution composed of 9.6parts by weight of sodium hydroxide, 100 parts by weight of water, and8.2 parts by weight of chlorine gas is gradually added to it,maintaining the reaction temperature below C. After stirring for an hourlonger, the solid which forms is filtered and washed with water untilfree of acid, then air dried to yield good technical quality6-rnethoxy-6-methyl-3-isopropyl-1,5,5 trichlorohydrouracil.

Other l-halogen hydrouracils which follow can be prepared similarly byreacting an equivalent amount of the appropriately substitutedhydrouracil with the corresponding halogen.

EXAMPLE 11 Percent 5,5 dichloro 3 isopropyl 6 methoxy 6methylhydrouracil 80.0 Alkyl naphthalene sulfonate, Na salt 2.0Partially desulfonated calcium lignin -sulfonate 0.5 Attapulgite clay14.5 Precipitated tricalcium phosphate 3.0

These components are blended, micropulverized until the particles areunder 50 microns in diameter, then reblended.

The same conditioning agents can be used to formulate wetta'ble powderswith the following compounds:

3 cyclohexyl-5 ,5 -dichloro-6 -me thoxy-6 -methy1hydroura cil 3-sec-butyl-5 ,5 dichloro-6-m eth-oxy-6 -methylhydroura cil 5 ,5-dichloro-6-methoxy-6-methyl-3-phenylhydrouracil 5 ,5 -dichloro-6-hydroxy-6-methyl-3-phenylhydrouraci1 S-tert-butyl-S ,5 -dichloro-6-methoxy-6 -methylhydrouracil3-cyclopentyl-5,S-dichloro-6-methoxy-6-methylhydrouracil5-chloro-3-cyclohexyl- 6-ep oxy-6-methyl-5-nitrohydrouracil 3-tert-butyl-5 ,5 -dibrorno-6-hydroxy-6-methylhydrouracil 5 ,5 -dichloro-6-ethoxy-6-methyl-3 -ph enylhydrouracil '6-2-chloroethoxy) -5, 5-dich1oro-6-methyl-3-phenylhydrouracil3-cyclohexyl-5,G-dimethylhydrouracil 6-acetoxy-3 -cyclopehtyl-5 ,5-dichloro-G-methylhydrouracil 6-methyl-3 -phenyl-5 ,5,6-trichlorohydrouracil 3 -butyl-5 -chloro-6-methylhydrouracil 3-4-diphenylyl) -5 ,5 -dichloro-6-methyl-6-propoxyhydrouracil 3-p-chlorophenyl-5 ,5 -dichloro-6-ethoxy-6-methylhydrouracil 5 ,5-dichloro-6 -meth oxy-.6-methyl-3-m-to1ylhydrouraci1 5 ,5-dichloro-3-ethyl-6-methoxyhydrouracil 3-norbornylmethyl-1,5 ,5,o-tetramethylhydrouracil 3-cyclopropyl-5 ,5-dichloro-1-isoamyl-6-methoxy-6- methylhydroura cil5,5-dichloro-3,6-dimethyl-G-ethoxyhydrouracil 5 ,5 -dichloro-3,6-dimethyl-6-isopropoxyhydrouracil 6-brorno-3-cyclohexyl-5,5-dichloro-6-methylhydrouracil 6-bromo-5 ,5-dichloro-6-methyl-3-phenylhydrouracil 6-methyl-3 -phenyl-5 ,5,6-tribromohydrouracil 3 4-biphenylyl -6-methyl-5 ,56-trichlorohydrouracil 3 -cyclohexylhydrouracil 5 -methyl-3-phenylhydrouracil 3 -p-chlorophenyl-5 methylhydrouracil 3(3,4-dichlorophenyl -5-methylhydrouracil 6-methy1-3 -phenylhydrouracil 5-methyl-3 1-naphthyl)hydrouracil 6-methyl-3 1-n aphthyl hydrouracil 3(4'-biphenylyl -5-methylhydrouracil 3 4-biphenylyl -6-methylhydrouracil6-methyl-3 -norbornylhydrouracil 3-bornyl-6-methylhydrouracil 5-bromo-3-(p-chlorophenyl -1-methylhydrouracil 5-bromo-6-cyclohexyl-3-methylhydroura cil 5-bromo-6-methyl-3-phenylhydrouracil 5-chloro-3-cyclohexyl-6-methylhydroura cil 5 -chloro-6-methyl-3 -phenylhydrouraci15-bromo-6-methyl-3- (Z-naphthyl hydrouracil 5-bromo-3 -(4'-biphenylyl)-6-methylhydrouracil 5-brom0-6-methyl-3 -norbornylhydrouracil5-bromo-6-hydroxy-3 -isopropyl-6-methylhydrouracil 5 -bromo-3-sec-butyl-6-hydroxy-6-methylhydrouracil 5 -b romo-6-hydroxy-6-methyl-3-phenylhydrouracil 5-bromo-3-cyclohexyl-6-hydroxy-6-rnethylhydrouracil5-chloro-6-hydroxy-3-isopropyl-6-methylhydrouracil 5-chloro-3-cyclohexyl-6-hydroxy-6-methylhydrouracil 5-chloro-6-hydroxy-6methyl-3-phenylhydrouracil6-acetoxy-3-(2,3-dibromopropyl)-5,5-dichloro-6ethylhydrouracil Theseformulations, applied at 20 pounds of active ingredient per acre in 100gallons of water per acre with conventional mechanical sprayers, giveexcellent control of grasses and broad-leaved weeds around lumber yardsand areas where vegetation creates a fire hazard. Such weeds asquackgrass, crabgrass, foxtail, Johnson grass, lambs-quarters, pigweed,velvet leaf, spurge and purslane are controlled.

When 3 cyclohexyl-S ,5 -dichloro-6-methoxy-6-methylhydrouracil isapplied as a pre-emergence wettable powder formulation at 1 to 2 poundsof active ingredient per acre, giant and yellow foxtail, crabgrass andchickweed are removed selectively without injury to established Bermudagrass. 1

EXAMPLE 12 Percent 5,5-dibromo-6-hydroxy-3-isopropyl-6-methylhydrouracil50.00 Dioctyl sodium sulfosuccinate concreted with 15% sodium benzoate1.00 Low viscosity methyl cellulose 0.25 Finely-ground ignitedmontmorillonoid clay,

(Pikes Peak clay) 48.75

These ingredients are blended, micropulverized until the particles areunder 50 microns in diameter, then reblended.

This formulation is applied at 40 pounds per acre in gallons of waterper acre to a stand of plants constituting a fire hazard around oilstorage tanks. The treatment gives excellent control of this plantgrowth. Such species as wild barley, ryegrass, yellow foxtail, vervain,cinquefoil, wild mustard, quackgrass, and seedling Johnson grass arecontrolled for an extended period.

This formulation, applied at 1 to 2 pounds of active ingredient per acreas a pre-emergence or directed postemergence spray, also gives excellentselective control of to established Weigela, an ornamental plant.

EXAMPLE 15 Percent 3-butyl-5,5-dichloro-6-methyl-6-propoxyhydrouracil 20Xylene 80 This composition is made by mixing the mutually solublecomponents together.

This composition, applied at 20 pounds of active ingredient per acre in80 gallons of diesel oil per acre gives excellent control of vegetationalong railroad rights of way. Quackgrass, crabgrass, annual bindweed,water grass, blackeyed Susan, carpetweed, and chickweed are controlled.

Other hydrouracils which can replace the active in this formulation are:

6-butoxy-3-sec-butyl-5 ,5 -dichloro-6-methylhydrouracil,6-dibromo-1,6-dimethyl-3-cyc1ohexy1-6-hydroxyhydrouracil6-acetoxy-3-cyclohexyl-5 ,5 -dichloro-1,6-dimethyl hydrouracil1-amyl-3-cyclohexyl-S-methylhydrouracil 3-sec-butyl-5 ,5,6,6-tetramethylhydrouracil 3-sec-butyl-5,6-dibutylhydrouracil6-acetoxy-3-cyclopentyl-5,S-dichloro-LG-dimethyL hydrouracil6-acetoxy-3-tert-butyl-5-chloro-l,5,6-trimethylhydrouracilS-tert-butyl-1,6-dimethyl-5,5,6-trichlorohydrouracil1,6-dimethyl-3-isopropyl-5 ,5 ,6-trichlorohydrouracil1,6-dimethyl-3-phenyl-5 ,5 ,6-trichlorohydrouracil3-sec-butyl-6-ethoxy-6-methyl-1,5 ,5 -trichlorohydrouracil3-buty1-5,S-dichloro-1-ethyl-6-methoxy-6-methylhydrouracil3-cyclopentyl-5,S-dichloro-1,6-dimethyl-6-methoxyhydrouracil3-isopropyl-1,5,6-trirnethy1hydrouracil5,5-dibromo-1,6-diethyl-6-hydroxy-3-isopropylhydrouracil 6-(2-chloroethoxy) -5, 5-dichloro-3 -isopropyl-6-methylhydrouracil 3 -sec-butyl-S ,5 -dichloro-6 chlorornethyl) -6-methylhydrouracil3-cyclohexyl-1,G-dimethylhydrouracil 3-sec-butyl-5 ,5-dibromo-6-methoxy-6-methylhydrouracil3-ethyl-6-methoxy-6-methyl-1,5,5-trichlorohydrouraci1 6-ethyl-3-isopropyl-6-methoxy-1,5,5-trichlorohydrouracil 1-bromo-3-butyl-5,5-dichloro-6-methoxy-6-methylhydrouracil3-sec-butyl-6-methoxy-6-methyl-1,5,5-trichloro hydrouracil3-sec-buty1-1-chloro-5 ,G-tn'methylenehydrouracil3-cyclohexyl-5-chloro-6-methoxy-S-methoxymethyl- 6-methylhydrouracil Anemulsifiable oil formulation is prepared by mixing these mutuallysoluble components together.

The composition is extended with 80 gallons of a herbicidal oil, such asLion Herbicidal Oil No, 6, to form a sprayable oil formulationcontaining 2%, by Weight, of active ingredient. When applied from apressure sprayer to 28 weeds infesting a one acre area railroad right ofway, good initial and residual control is obtained of mixed vegetationincluding such weeds as ragweed, pigweed, daisy, lambs quarters,crabgrass, foxtail, quackgrass, cheat, witch grass, Jimson weed, andbutton weed.

Other compounds which can replace the active in this formulationinclude:

6 -butoxy-5 5-dichloro-6-methyl-3 -phenylhydrouracil 3-cyclohexyl-1,6-dimethyl-5 ,5 ,6-trichlorohydrouracil 3 -isopropyl-5,6trimethylenehydrouracil 3 -tert-butyl-5, 5 -dichloro- 1,6-dimethyl-6-ethoxyhydrouracil 3 -sec-butyl-5S-dichloro-1,6-dimethyl-6-ethoxyhydrouracil 55-dichloro-6-ethoxy-1-ethy1-6-methyl-3 -phenylhydrouracil 6-2-chloroethoxy) -5 ,5 -dichloro-1-ethyl-6-methyl- 3 -phenylhydrouracil 3-sec-buty1-1-methy1-5,6-trimethylenehydrouracil 3-cyclohexyl-1,6-dimethyl-S-methoxyrnethylhydrouracil 3 -tert-butyl-l,6-dimethyl-5 -methoxymethylhydrouracil 3 -sec-butyl-5 ,5 -dibromo-1,6-dimethyl-6- hydroxyhydrouracil 3-sec-butyl-1,6-dimethyl-5-ethoxymethylhydrouracil5-chloro-3-cyclohexyl-1,6-dirnethylhydrouracil 5 ,5 -dichloro-l,6-dimethy-l-3-isopropyl-6- methoxyhydrouracil 3-butyl-5 ,5 -dichloro-1-ethyl-6-methoxy-6- methylhydrouracil 3 -cycloheXyl-5 ,5 -clichlorol,6-dimethyl-6- methoxyhydrouracil5,5-dichloro-1,G-dimethyl-6-methoxy-3-phenylhydrouracil 3-isopropyl-1,5,6-trimethylhydrouracil 6-acetoxy-5 ,5 -dichloro-3-3-methoxypropyl -6- methylhydrouracil 6-acetoxy-3-cyclohexy1-5 ,5-dichloro-1 ,6-

dimethylhydrouracil 3 -cyclohexyl-1, 6-dimethyl-5 ,5 ,6-trichlorohydrouracil 1,5 -dimethyl-3 -isopropylhydrouracil 3-cyclohexyll 5-dimethy1hydrouracil 3-butyl-6-methylhydrouracil 3-sec-butyl-6-methylhydrouracil 1 ,6-dimethyl-3-norbornylhydrouracil 5-bromo-3-isopropyl-6-methylhydrouracil 5-bromo3-butylhydrouracil5-bromo-3-sec-butyl-6-methylhydrouracil5-bromo-3-cyclohexyl-1,6-dimethylhydrouracil 5-chloro-3-isopropyl-6-methylhydrouracil3-sec-butyl-5-chloro-6-methylhydrouracil1,6-dimethyl-3-norbornylhydrouracil 6-butoxy-3- 3,4-dibromophenyl) -5 ,5-dichloro-6- methylhydrouracil 5 ,5 -di chloro-3-ethoxy-6-methoxy-6-methylhydrouracil 5 -chloro-S-ethoxymethyl-6-hydroxy-6-methyl-3 phenylhydrouracil 5 ,5-dichloro-6-hydroxy-6-rnethyl-3- Z-naphthyl hydrouracil 3-(p-bromophenyl) -5 ,5 -dichloro-6-hydroxy-3- isopropylhydrouracil EXAMPLE17 Percent 3-isopropyl-1,5,5-trichloro-6-meth0xy- G-methylhydrouracil 3OTrimethyl nonyl ether of polyethylene glycol 30 Polyoxyethylene ethersplus oil soluble sulfonates 5 Isophorone 35 Other compounds which canreplace the active component in this formulation are:

EXAMPLE 18 Percent 3-cyclohexyl-5,5-dichloro 6-methoxy-6-methylhydrouracil 20 Sodium dodecyl benzene sulfonate 35 Synthetic finecalcium silicate 45 These components are blended and micropulverizeduntil the hydrouracil particles are under 50 microns in diameter. Thiscomposition is applied as a directed postemergence spray at the rate of1.5 pounds of active ingredient and 2.6 pounds of surfactant per acre in35 gallons of water to a vigorously growing population of annual weedsgrowing in sugarcane.

Excellentcontrol of velvet leaf, lambs-quarters, water grass, crabgrass,foxtail, and annual morning-glory is obtained:

EXAMPLE 19 Percent 5,5-dichlor-3-isopropyl-6-rnethoxy-6methylhydrouracil 80.0 Alkyl naphthalene sulfonate, Na salt 2.0Partially desulfonated calcium lignin sulfonate .5 Attapulgite clay 14.Precipitated tricalcium phosphate 3.0

These ingredients are blended and micropulverized until the hydrouracilparticles are under 50 microns in diameter.

Fifteen pounds of this formulation is mixed with 6 pounds oftrimethylnonyl polyethylene glycol ether in 60 gallons of water.

This mixture is applied to a fence-row infested with crabgrass, foxtail,barnyard grass, pigweed, lambsquarters and wild mustard. The treatmentgives quick contact kill of the vegetation with excellent residualcontrol.

EXAMPLE 20' 5-chloro 6-ethoxy-3-isopropyl-6-rnethyl-5 nitrouracil may besubstituted for the 5,5-dichloro-3-isopropyl-6-methoxy-6-methylhydrouracil in Example 19. The resulting wettable powdermay be made up to spray concentration with water. When sprayed over anewly planted corn field at 2 pounds active per acre, excellent controlof weeds such as mustard, pigweed, chickweed, and crab grass is obtainedWithout injury to the corn.

Attapugite clay 30 EXAMPLE 21 5,5 dichloro-6-ethoxy-3 isopropyl6-rnethylhydrouracil may be'substituted for the5,5-dichloro-3-isopropyl- 6-methoxy-6-methylhydrouracil in Example 20above. This formulation is applied at rates of 1% pounds of active peracre to a newly seeded field of flax. Excellent control of weeds such asvelvet leaf, wild buckwheat, mustard, fiower-of-an-hour, crab grass, andseedling Johnson grass is obtained with no observable injury to theflax. t

' EXAMPLE 22 5-chloro 3 isopropyl-6-methoxy-6-methyl-5-nitrohydrouracilis substituted for the 5,5-dichloro-6-ethoxy-3-isopropyl-G-methylhydrouracil in Example 21 above. The formulation isapplied at rates'of 3 pounds of active per acre as an aqueous suspensionto a newly planted field of peanuts. Excellent control of such Weeds aschickweed, corn cockle, mustard, velvet leaf, crabgrass, and seedlingcocklebur is obtained with no observable injury to the peanuts.

EXAMPLE 23 Percent 5,5-dichloro 3-isopropyl-6-methoxy-6-methylhydrouracil 3- 3 ,4'-dichlorophenyl) -1,1-dimethylurea r 40 Alkylaryl polyetheralcohol 40% extended on a silica powder 4Substitutedacetylenic glycol 1 Partially desulfonated sodium ligninsulfonate 2 Kaolin clay 10 Synthetic fine silica 3 These components areblended in a ribbon blender, micropulverized until the particles areunder 50 microns in diameter, then reblended. i

This formulation is added to gallons of water and applied at the rate of25-pounds of active ingredient per acre for the control of spurge,beggartick, goldenrod, broomsedge, barnyard grass, crabgass, and lovegrass growing in lumber yards. This treatment gives excellent killoffoliage and has extended residual activity in the soil.

EXAMPLE 24- 3-sec-butyl-5,5-dichloro-6 methoxy-6 methylhy v drouracil32.00 2-chloro-4-ethylamino 6- isopropylamino-s-triazine 48.00 Alkylnaphthalene sulfonic acid 1.75 Methyl cellulose 0.25 18.00

These components are blended in a ribbon blender, micropulverized untilthe particles are under 50 microns in diameter, then reblended.

This formulation is applied in gallons of Water at the rate of 21 poundsof active ingredients per acre for the control of broadleaf and grassspecies growing along ditch banks. A spring application to vigorousgrowing weeds gives outstanding control of bromegrass, ryegrass,crabgrass, qu-ackgrass, common ragweed, speedwells, broadleaf plantain,oxeye daisy, and dandlelion.

EXAMPLE 25 Percent 5,5-dibromo 6 hydroxy-3-isopropyl-6-methylhydrouracil5-bromo-3-sec-butyl-6-methyluracil 25 Oleyl ester of sodium isothionate1 Alkyl naphthalene sulfonic acid, Na salt 1 Kaolin clay 20 Syntheticfine silica 3 These components are blended in a ribbon blender,micropulverized until the particles are under 50 microns in diameter,then reblended.

This formulation is used for-the control of weeds These components arewet-milled until the particle diameters are under 5 microns.

- This formulation is applied to lawn areas at a rate of 4 pounds ofactive ingredients per acre. Crabgrass, annual bluegrass, chickweed,pigweed, foxtail, and white clover is controlled selectively withoutinjury to established Bermuda grass.

. EXAMPLE 27 Percent 3-sec-butyl-5 ,5-dichloro-6-ethoxy-6-methylhydrouracil E 30.0

Lignin sulfonates, Ca, Mg salts 10.0

Bentonite (swelling type) 2.0 Sodium pentachlorophenate 1.0 Disodiumhydrogen phosphate 1.0

Water 56.0

The-components are sand-milled until the particle diameters are under 5microns.

This formulation may be extended with water and sprayed to control weedsgrowing along a right of way. When ,used at the rate of 25 pounds peracre in the spring, excellent control of such weeds as crabgrass, annualbluegrass, chickweed, pigweed, and foxtail is obtained.

EXAMPLE 28 I Percent 6-butoxy-5,5-dichloro-6-methyl-3-phenylhydrouracil40 2,4,5-trichlorophenoxy acetic acid propylene glycol butyl ether ester10 Mixed polyoxyethylated sorbitan monooleate and ethylene diaminedodecyl benzene sulfonate 5 Synthetic fine silica 45 These ingredientsare blended, micropulverized, and reblended.

The resulting oil dispersible powder is used for maintainingweed-f-reeareas along electric power line rights of way. An application of 18pounds of active ingredient per acre in 60 gallons of diesel oil givesexcellent control of purple top, crabgrass, poison ivy, blackberry,honeysuckle, butter and eggs, and horse nettle.

EXAMPLE 29 Percent 5,6-dimethyl-3-isopropylhydrouracil 3.31,1-dimethyl-3-phenylurea 6.7 California Ca, Mg sub-bentonite 75.0Anhydrous sodium sulfate 15.0

These components are blended, micropulverized, pugmilled with about 20%water, moist granulated, dried and screened to 15-30 mesh granules.

The composition is applied by hand around isolated clumps of brush,using 2 teaspoonsful of material per clump. Oak seedling, mapleseedlings, willow trees, winged elm and sweet gum are controlled.

EXAMPLE 30 Percent 5,5-dichloro-6-ethoxy-3-isopropyl-6 methylhydrouracil15 2,3,6-trichlrobenzoic acid, Na salt Anhydrous sodium sulfateCalifornia su-b-bentonite 70 These ingredients are blended andmicropulverized until the particles are under 50 microns in diameter.The lend is then pug-milled with 1520% water and extruded throughAz-inch to -inch holes. These extrusions are cut into /s-inch lengthsand dried.

This formulation is useful for controlling perennial and woody vines.

An application of 20 pounds of active ingredient per acre givesexcellent control of broomsedge, Indian grass, purple top, Virginiacreeper, annual bindweed and isolated clumps of honeysuckle.

EXAMPLE 31 Twelve pounds of 5'chloro-3-isopropyl-6-methoxy-6methyl-5-nitrohydrouracil as an wettable powder and 3 pounds of4,S-dinitro-ortho-sec-butylphenol in 4 gallons of em-ulsifiable oil areblended as a tank mix and applied at the rate of 15 pounds of activeingredient per acre in 80 gallons of water to annual and perennial weedsgrowing along a fence row. Good kill with'excellent residual weedcontrol is obtained.

2,2-dischloropr0pionic acid, sodium salt at 15 pounds per acre orammonium sulfamate at 35 pounds per acre can be substituted for4,6-dinitro-ortho-sec-butylphenol with satisfactory results.

EXAMPLE 32 3-sec-butyl-5,5-dichloro-6-methoxy 6-methylhydrouracil istank mixed with herbicidal oil at a concentration of 12 pounds pergallons to form a homogeneous solution which is then sprayed on mixedweeds on a railroad right of way. When applied at the rate of 12 poundsactive per acre quick kill of red sorrel, lovegrass, quackgrass,pigweed, plantain, and sweet clover is obtained. Re-establishment ofseedling weeds is effectively delayed. I

The compounds listed under Example 15 can be used in like manner.

EXAMPLE 33 Percent 3-sec-butyl-5,5-dichloro-6-methoxy-6methylhydrouracil 99.0 Trimethylnonyl polyethylene glycol ether 1.0

The ingredients are mixed in a ribbon blendor and then micropulverizedthrough a coarse screen.

Any of the compounds of this invention can be formulated in the samemanner. The resulting high-strength composition can be used in place ofthe technical hydrouracil in any of the formulation examples.

I claim:

1. A compound selected from (a) compounds of the formula wherein R isselected from the group consisting of alkyl of 3 through 6 carbon atoms,cycloalkyl of 3 through 12 carbon atoms, optionally substituted with asubstituent selected from the group consisting of alkyl of 1 through 4carbon atoms, methoxy, chlorine, and bromine, cycloalkyl of 4 through 13carbon atoms, optionally substituted with a substituent selected fromthe group consisting of alkyl of 1 through 4 carbon atoms, methoxy,chlorine, and bromine;

R is selected from the group consisting of chlorine, bromine, fluorine,nitro, methyl, ethyl, hydroxymethyl, methoxymethyl, ethoxymethyl,methoxy, and hydrogen;

R is selected from the group consisting of chlorine and bromine;

33 R is selected from the group consisting of alkoxy of 1 through 6carbon atoms, and haloalkoxy of 1 through 6 carbon atoms; and R isselected from the group consisting of methyl and ethyl; and (b) phenolcomplexes of the compounds of (a) having the formula H O X 0 H R2 BIN 10H R5 n wherem 15 R R R R and R are as defined above,

X is selected from the group consisting of hydrogen, chlorine, bromine,nitro, alkyl of 1 through 3 carbon atoms, and alkoxy of 1 through 3carbon atoms, 20

Y is selected from the group consisting of chlorine and alkyl of 1through 3 carbon atoms, In is a Whole number 1 through 5, and

n is selected from the group consisting of 1 and 2.5,5-dichloro-3-isopropyl-6-methoxy-6 methylhydrouracil.

3. 5,5-dichloro-3-isopropyl-6-ethoxy 6 methylhydrouracil.

4. 5,5-dichloro-3-cycloheXyl-6-methoxy 6 methylhydrouracil.

5. 3-sec-butyl-5,5-dichloro-6-methoxy-6 methylhydro uracil.

6. 3-sec-butyl-5,5-dichloro-6-ethoxy 6 methylhydrouracil.

7. 3-tert-butyl-5,5-dichloro-6-methoxy 6 methylhydrouracil.

8. 5,5-dichloro-6-methoxy-6-methyl 3 (3-penty1)hydrouracil.

9. 5,5-dichloro-6-ethoxy-6-methyl 3 phenylhydrouracil.

No references cited.

NICHOLAS S. RIZZO, Primary Examiner.

F. A. MIKA, Assistant Examiner.

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No.3,360,523 December 26, 1967 Harvey M. Loux It is hereby certified thaterror appears in the above numbered patent requiring correction and thatthe said Letters Patent should read as corrected below.

1k lColumn 32, line 65, for "cycloalkyl" read cycloalkyl a y Signed andsealed this 21st day of January 1969.

(SEAL) Attest:

EDWARD J. BRENNER Commissioner of Patents Edward M. Fletcher, Jr.

Attesting Officer

1. A COMPOUND SELECTED FROM (A) COMPOUNDS OF THE FORMULA